Alpha furyl aldehyde sulphonates



R, R2,,Ra and R4 are hydrogen or Patented June 18, 1946 UNITED STATES PATENT OFFICE Jack T. Thurston, Riverside,

American Cyanamld Company,

Conn, asslgnor to New York, N. Y.,

a corporation oi Maine No Drawing. Application October 6, 1944,

Serial No. 557,562

1 Claim. (Cl. 260-445) 1 2 This invention relates to certain new and usemay be prepared by condensing 1 mol of furiural ful compounds and to their preparation. More particularly, my invention relates to furyl substituted organic sulphonates.

An object of this invention phonates which contain a furyl group as stituent.

Another object of this invention is to provide organic sulphonates suitable for the'preparation of resins having cation active properties.

A further object of my invention is to provide processes for preparing the aforementioned sulphonates.

The compounds which form the subject of this invention have the following general formula:

is to provide sula sub- L cn cnax $M where X is an activatinggroup possessing a polar bond, e. g.

. H c- COOR, '-CONRR,,'CN, NOz; and where M is a metal or hydrogen or H'NR2R3R4 where organic radicals. More particularlymost of the compounds of this invention have'the formula H kO: (|lH-CHR-CH r 5.1M where R i defined as 'above. The term "sulphonate as used herein is intended to cover the hydrogen sulphonatc as well as the metal, ammonia or amine salts thereof.

Thesulphonates described above may be prepared by treating a compound of the following formula: I

where X and R are the same as before. with a bisulphite or with sulphur dioxide in a suitable mewith 1 mol of a substance containing an active methyl group or an active methylene group, e. g.

compounds having the formula:

Hz(|7R x '(where R and X are defined in the same manner as above) or vinylogs thereof.

The following examples inwhich the proportions are in parts by weight, except as otherwise indicated, are given by way of illustration .and not in limitation and the furfural is 95% pure.

EXAMPLE Preparation of 3-potassiumsulpho-3-alpha-furylpropanal v v Parts Impure 3-alpha-furylacrolein 80 Potassium metabisulphite 69 Water 100 The 3-alpha-furylacrolein contains a small proportion of impurities. A mixture of the substances tabulated is heated in a suitable reaction vessel surrounded by a. steam bath and provided foregoing example that 1 mol of furfural reacts with 1 mol of a substance containing an active methyl group oran active methylene group and the resulting compound in turn reacts with 1 mol of a bisulphite or sulphurous acid. 'It may be desirable, oi'course, in some instances to employ an excess of one of the reactants in order to drive the reaction to completion.

Other aldehydes having an active methyl group or an active methylene group may be combined with furfural and converted to the sulphonate in accordance with the foregoing disclosure. Thus, for example, other aldehydes may beused, e. g. chloracetaldehyde, brom'acetaldehyde, crotonaldehyde, sorbic aldehyde, propionaldehyde, heptaldehyde, succinic aldehyde, phenylacetaldehyde, sulphophenylacetaldehyde, and the like.

The solid mass is broken up.

Compounds havingt'lie general formula:

phite. In general the alkali metal bisulphltes are preferred. The hydrogen sulphonates may be converted into the corresponding metal, ammonium or amine salts if desired. Examplesof amines for such salts are: methyl amine, dimethyl amine, pyridine, triethyl amine, the mono-, diand tri-eth'anolamines, etc. Another method of producing the sulphonates is by treatment oi the furfurylidene compounds with a hydrogen halide followed by treatment withsodium sulphite or with the alkali metal sulphites. Thus, for example, hyldrogen chloride may be added to ,2-alpha-furylacrolein and the resulting material treated with sodium sulphite. Still another type of sulphonate may be prepared by the condensation of furi'ural with a halogen substituted aldehyde such as chloracetaldehyde, followed by treatment (1) with a hydrogen haliue and then with a sulphite or (2) with an equimolecular mixture of a bisulphite and a sulphlte. The bisulphite or sulphite may be a salt of an alkali metal, ammonia, or any other desired metal orv amine.

The sulphonates may be prepared from the furfurylidene compounds by reaction with bisulphite at temperatures ranging upwardstrom room tem-- perature. In most instances, the reaction is advantageously carried out at atemperature between about 70 C. and about 130 C. If sulphur dioxide be used, the reaction is preferably carried out under pressure, e. g. 25-100 pounds per sq. in., and/or at relatively low temperatures such as about 20 C. The time of reaction varies somewhat according to the compatibility of the reactants. Thus, it a homogeneous solution 6; the reactants be employed, the reaction will usually be completed in km about 5 hour to about 2 hours.

On t1 .e other hand, if the solution oi. the reactants is not homogeneous, 6-8 hours or even more may be required. Generally, water is employed as the solvent medium for the bisulphite and the lurfurylidene compound but if sumcient solubility is not obtained other solvents may be used. Mixtures of water and water-miscible organic soivents are especially suitable since the water is a good solvent for the bisulphite, while the organic solvent is a 800d solvent for the furfuylidene com-- pound. Examples of suitable solvents are methanol, ethanol, propanol, isopropanol, tertiary butanol, dioxane, the lower alkyl mono-ethers of ethylene glycol and diethylene glycoLsuch as the mono-ethyl ether of ethylene glycol, the monobutyl ether of di-ethylene glycol, etc. Furthermore, inert ketones may be employed as solvents for the reactants in the production 01' the sulphonates. In some instances it may be desirable to employ active ketones as intermediates in the preparation or the sulphonates. Thus, the 'bisulphite may add to an active ketone and this in turn reacts with the furfurylidene compound, the former giving up the bisulphite to the latter.

My ruryl substituted sulphonic acids are especially suitable for resiniflcation with an aldehyde to produce resinous materials having. cation active properties. They are also useful in the preparation of emulsifiers, wetting agents, dispersing agents and asiintermediates in the synthesis of many other organic compounds.

This application is a continuation-in-part of my copending application Serial No. 453,277, filed Au ust 1, 1942. I

Obviously, many modifications and variations in the processes and compositions described above may be made without departing from the spirit and scope of the invention as defined in the appended claim.

JACK T. THUMTON. 

